Gold(I) and palladium(II) complexes of 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene "click" carbenes: systematic study of the electronic and steric influence on catalytic activity

James R Wright; Paul C Young; Nigel T Lucas; Ai-Lan Lee; James D Crowley

doi:10.1021/om400773n

Gold(I) and palladium(II) complexes of 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene "click" carbenes: systematic study of the electronic and steric influence on catalytic activity

James R Wright, Paul C Young, Nigel T Lucas, Ai-Lan Lee^*, James D Crowley

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

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Abstract

The synthesis of a small family of six electronically and sterically modified 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene gold(I) chloride complexes is described. Additionally, the corresponding trans-[PdBr2(iPr2-bimy)(1,3,4-trisubstituted 1,2,3-triazol-5-ylidene)] complexes are also generated and used to examine the donor strength of the 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene ligands. All compounds have been characterized by (1)H and (13)C NMR and IR spectroscopy, high-resolution electrospray mass spectrometry (HR-ESI-MS), and elemental analysis. The molecular structures of four of the gold(I) and four of the palladium(II) complexes were determined using X-ray crystallography. Finally, it is demonstrated that these 1,2,3-triazol-5-ylidene gold(I) chloride complexes (Au(trz)Cl) are able to catalyze the cycloisomerization of 1,6-enynes, in high yield and regioselectivity, as well as the intermolecular direct etherification of allylic alcohols. Exploiting the Au(trz)Cl precatalysts allowed the etherification of allylic alcohols to be carried out under milder conditions, with better yield and regioselectivity than selected commercially available gold(I) catalysts.

Original language	English
Pages (from-to)	7065-7076
Number of pages	12
Journal	Organometallics
Volume	32
Issue number	23
DOIs	https://doi.org/10.1021/om400773n
Publication status	Published - 9 Dec 2013

Keywords

N-HETEROCYCLIC CARBENES
NORMAL 1,2,3-TRIAZOLYLIDENE LIGANDS
AZIDE-ALKYNE CYCLOADDITION
HOMOGENEOUS AU-CATALYSIS
ONE-POT SYNTHESIS
C MULTIPLE BONDS
WATER OXIDATION
1,4-DISUBSTITUTED 1,2,3-TRIAZOLES
COPPER(I) COMPLEXES
MONOALLYLIC DIOLS

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10.1021/om400773n

Gold(1) and Palladium (II) Complexes
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title = "Gold(I) and palladium(II) complexes of 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene {"}click{"} carbenes: systematic study of the electronic and steric influence on catalytic activity",

abstract = "The synthesis of a small family of six electronically and sterically modified 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene gold(I) chloride complexes is described. Additionally, the corresponding trans-[PdBr2(iPr2-bimy)(1,3,4-trisubstituted 1,2,3-triazol-5-ylidene)] complexes are also generated and used to examine the donor strength of the 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene ligands. All compounds have been characterized by (1)H and (13)C NMR and IR spectroscopy, high-resolution electrospray mass spectrometry (HR-ESI-MS), and elemental analysis. The molecular structures of four of the gold(I) and four of the palladium(II) complexes were determined using X-ray crystallography. Finally, it is demonstrated that these 1,2,3-triazol-5-ylidene gold(I) chloride complexes (Au(trz)Cl) are able to catalyze the cycloisomerization of 1,6-enynes, in high yield and regioselectivity, as well as the intermolecular direct etherification of allylic alcohols. Exploiting the Au(trz)Cl precatalysts allowed the etherification of allylic alcohols to be carried out under milder conditions, with better yield and regioselectivity than selected commercially available gold(I) catalysts.",

keywords = "N-HETEROCYCLIC CARBENES, NORMAL 1,2,3-TRIAZOLYLIDENE LIGANDS, AZIDE-ALKYNE CYCLOADDITION, HOMOGENEOUS AU-CATALYSIS, ONE-POT SYNTHESIS, C MULTIPLE BONDS, WATER OXIDATION, 1,4-DISUBSTITUTED 1,2,3-TRIAZOLES, COPPER(I) COMPLEXES, MONOALLYLIC DIOLS",

author = "Wright, {James R} and Young, {Paul C} and Lucas, {Nigel T} and Ai-Lan Lee and Crowley, {James D}",

year = "2013",

month = dec,

day = "9",

doi = "10.1021/om400773n",

language = "English",

volume = "32",

pages = "7065--7076",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "23",

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TY - JOUR

T1 - Gold(I) and palladium(II) complexes of 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene "click" carbenes

T2 - systematic study of the electronic and steric influence on catalytic activity

AU - Wright, James R

AU - Young, Paul C

AU - Lucas, Nigel T

AU - Lee, Ai-Lan

AU - Crowley, James D

PY - 2013/12/9

Y1 - 2013/12/9

N2 - The synthesis of a small family of six electronically and sterically modified 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene gold(I) chloride complexes is described. Additionally, the corresponding trans-[PdBr2(iPr2-bimy)(1,3,4-trisubstituted 1,2,3-triazol-5-ylidene)] complexes are also generated and used to examine the donor strength of the 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene ligands. All compounds have been characterized by (1)H and (13)C NMR and IR spectroscopy, high-resolution electrospray mass spectrometry (HR-ESI-MS), and elemental analysis. The molecular structures of four of the gold(I) and four of the palladium(II) complexes were determined using X-ray crystallography. Finally, it is demonstrated that these 1,2,3-triazol-5-ylidene gold(I) chloride complexes (Au(trz)Cl) are able to catalyze the cycloisomerization of 1,6-enynes, in high yield and regioselectivity, as well as the intermolecular direct etherification of allylic alcohols. Exploiting the Au(trz)Cl precatalysts allowed the etherification of allylic alcohols to be carried out under milder conditions, with better yield and regioselectivity than selected commercially available gold(I) catalysts.

AB - The synthesis of a small family of six electronically and sterically modified 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene gold(I) chloride complexes is described. Additionally, the corresponding trans-[PdBr2(iPr2-bimy)(1,3,4-trisubstituted 1,2,3-triazol-5-ylidene)] complexes are also generated and used to examine the donor strength of the 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene ligands. All compounds have been characterized by (1)H and (13)C NMR and IR spectroscopy, high-resolution electrospray mass spectrometry (HR-ESI-MS), and elemental analysis. The molecular structures of four of the gold(I) and four of the palladium(II) complexes were determined using X-ray crystallography. Finally, it is demonstrated that these 1,2,3-triazol-5-ylidene gold(I) chloride complexes (Au(trz)Cl) are able to catalyze the cycloisomerization of 1,6-enynes, in high yield and regioselectivity, as well as the intermolecular direct etherification of allylic alcohols. Exploiting the Au(trz)Cl precatalysts allowed the etherification of allylic alcohols to be carried out under milder conditions, with better yield and regioselectivity than selected commercially available gold(I) catalysts.

KW - N-HETEROCYCLIC CARBENES

KW - NORMAL 1,2,3-TRIAZOLYLIDENE LIGANDS

KW - AZIDE-ALKYNE CYCLOADDITION

KW - HOMOGENEOUS AU-CATALYSIS

KW - ONE-POT SYNTHESIS

KW - C MULTIPLE BONDS

KW - WATER OXIDATION

KW - 1,4-DISUBSTITUTED 1,2,3-TRIAZOLES

KW - COPPER(I) COMPLEXES

KW - MONOALLYLIC DIOLS

U2 - 10.1021/om400773n

DO - 10.1021/om400773n

M3 - Article

C2 - 24353365

SN - 0276-7333

VL - 32

SP - 7065

EP - 7076

JO - Organometallics

JF - Organometallics

IS - 23

ER -

Gold(I) and palladium(II) complexes of 1,3,4-trisubstituted 1,2,3-triazol-5-ylidene "click" carbenes: systematic study of the electronic and steric influence on catalytic activity

Abstract

Keywords

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